U.S. patent number 4,210,390 [Application Number 05/919,607] was granted by the patent office on 1980-07-01 for electrochromic composition and electrochromic display device using same.
This patent grant is currently assigned to Dai Nippon Toryo Co., Ltd.. Invention is credited to Masachika Yaguchi.
United States Patent |
4,210,390 |
Yaguchi |
July 1, 1980 |
Electrochromic composition and electrochromic display device using
same
Abstract
An electrochromic composition is composed of a solvent, an
electrochromic compound having a high solubility to the solvent,
and a compound selected from a group of ammonia, organic amine and
alkali. The solubility of the electrochromic compound to the
solvent is not less than 10.sup.-2 mol/100 g-solvent in a reduced
state and not less than 10.sup.-1 mol/100 g-solvent in an oxidized
state. A masking agent may be added to the EC compound. The EC
composition is sealed in an EC display cell.
Inventors: |
Yaguchi; Masachika (Yokohama,
JP) |
Assignee: |
Dai Nippon Toryo Co., Ltd.
(Osaka, JP)
|
Family
ID: |
26401774 |
Appl.
No.: |
05/919,607 |
Filed: |
June 27, 1978 |
Foreign Application Priority Data
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Jun 28, 1977 [JP] |
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52-76114 |
May 22, 1978 [JP] |
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53-60721 |
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Current U.S.
Class: |
359/273;
252/600 |
Current CPC
Class: |
G02F
1/1503 (20190101); C09K 9/02 (20130101) |
Current International
Class: |
C09K
9/02 (20060101); G02F 1/15 (20060101); G02F
1/01 (20060101); G02F 001/17 (); G09F 009/30 () |
Field of
Search: |
;350/357
;252/408,518,300 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2449278 |
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Apr 1975 |
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DE |
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2707099 |
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Aug 1977 |
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DE |
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51-23488 |
|
Feb 1976 |
|
JP |
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51-44897 |
|
Apr 1976 |
|
JP |
|
52-100381 |
|
Aug 1977 |
|
JP |
|
Other References
Kawata, T. et al., Jap. J. Appl. Phys., vol. 14, No. 5, pp. 725-726
(1975)..
|
Primary Examiner: Gron; Teddy S.
Attorney, Agent or Firm: Ferguson, Jr.; Gerald J. Baker;
Joseph J.
Claims
I claim:
1. An electrochromic composition comprising a solvent, an
electrochromic compound which is colored in a reduced state, the
solubility to the solvent of which is not less than 10.sup.-2
mol/100 g-solvent in said reduced state and not less than 10.sup.-1
mol/100 g-solvent in an oxidized state, and an additive compound
selected from the group consisting of (a) ammonia, (b) an amine
where all substituents thereof are radicals selected from the group
of aliphatic radicals, alicyclic radicals and aromatic radicals and
(c) an alkali compound selected from the group consisting of
hydroxides, carbonates, and phosphates, said electrochromic
compound occurring in said reduced state and the solution of the
reduced electrochromic compound being basic due to the presence of
said additive compound.
2. An electrochromic composition according to claim 1 further
comprising a masking agent.
3. An electrochromic composition according to claim 1 or 2, wherein
said radical is an aliphatic radical.
4. An electrochromic composition according to claim 3 wherein said
amine is represented by the general formula R--NH.sub.2 and R is
said aliphatic radical.
5. An electrochromic composition according to claim 3 wherein said
amine is represented by the general formula ##STR9## where R and R'
are said aliphatic radicals.
6. An electrochromic composition according to claim 1 or 2, wherein
said radical is an aromatic radical.
7. An electrochromic composition according to claim 1 or 2, wherein
said alkali compound is sodium hydroxide.
8. An electrochromic composition according to claim 1 or 2, wherein
said alkali compound is potassium hydroxide.
9. An electrochromic display device comprising an electrochromic
display cell and an electrochromic composition filled in said cell,
said electrochromic composition comprising a solvent, an
electrochromic compound which is colored in a reduced state, the
solubility of the solvent of which is not less than 10.sup.-2
mol/100 g-solvent in said reduced state and not less than 10.sup.-1
mol/100 g-solvent in an oxidized state, and an additive compound
selected from the group consisting of (a) ammonia, (b) an amine
where all substituents thereof are radicals selected from the group
of aliphatic radicals, alicyclic radicals and aromatic radicals and
(c) an alkali compound selected from the group consisting of
hydroxides, carbonates, and phosphates, said electrochromic
compound occurring in said reduced state and the solution of the
reduced electrochromic compound being basic due to the presence of
said additive compound.
10. An electrochromic display device according to claim 9 wherein
said electrochromic composition further comprises a masking
agent.
11. A device as in claim 9 where said additive compound is selected
from the group consisting of said ammonia and said amine.
12. An electrochromic display device according to claims 9 or 11
wherein said electrochromic compound is an acid salt compound.
13. An electrochromic display device according to claim 12 wherein
said amine is water soluble.
14. A composition as in claim 1 where said additive compound is
selected from the group consisting of said ammonia and said
amine.
15. A composition as in claims 1 or 14 where said solvent is
selected from the group consisting of (a) water, (b) water and
alcohol, and (c) water and alcohol to which a small amount of
ester, ketone, or alkyl benzene is added.
16. A composition as in claim 15 where said electrochromic compound
is selected from the group consisting of pyridine derivatives,
bipyridinium derivatives, phenazine derivatives, aminoquinone
derivatives, rhodamine derivatives, and diphthalocyanine
derivatives.
17. A composition as in claim 16 where said electrochromic compound
is present within the range of 0.1 to 10 wt.% of said composition,
and preferably within the range of 1 to 5 wt.%.
18. A composition as in claims 1 or 14 where the said
electrochromic compound is alkyl bipyridinium salt, it being so
reduced by said additive compound that one mono anion thereof is
trapped.
19. A composition as in claim 18 where the number of mols of said
additive compound is no more than the number of mols of the mono
anion of the alkyl bipyridinium salt.
20. A device as in claims 9 or 11 where said solvent is selected
from the group consisting of (a) water, (b) water and alcohol, and
(c) water and alcohol to which a small amount of ester, ketone, or
alkyl benzene, is added.
21. A device as in claim 20 where said electrochromic compound is
selected from the group consisting of pyridine derivatives,
bipyridinium derivatives, phenazine derivatives, aminoquinone
derivatives, rhodamine derivatives, and diphthalocyanine
derivatives.
22. A device as in claim 21 where said electrochromic compound is
present within the range of 0.1 to 10 wt.% of said composition, and
preferably within the range of 1 to 5 wt.%.
23. A method of operating an electrochromic display device
comprising a pair of oppositely disposed electrode plates each
bearing on the inner surface thereof an electrode and an
electrochromic composition sealed between said pair of oppositely
disposed electrode plates, said electrochromic composition
comprising an electrochromic compound which is colored in a reduced
state and a solvent, the solubility of said electrochromic compound
to said solvent being not less than 10.sup.-2 mol/(100g solvent) in
said reduced state and not less than 10.sup.-1 mol/(100g solvent)
in an oxidized state, and an additive selected from the group
consisting of (a) ammonia, (b) an amine where all substituents
thereof are radicals selected from the group of aliphatic radicals,
alicyclic radicals and aromatic radicals, and (c) an alkali
compound selected from the group consisting of hydroxides,
carbonates, and phosphates, said electrochromic compound occurring
in said reduced state and the solution of the reduced
electrochromic compound being basic due to the presence of said
additive compound, said method comprising the steps of
energizing said device by applying an electrical potential across
said plates and
extinguishing said device by only removing said potential
therefrom.
24. A method as in claim 23 where said additive compound is
selected from the group consisting of said ammonia and said
amine.
25. A method as in claims 23 or 24 where said solvent is selected
from the group consisting of (a) water, (b) water and alcohol, and
(c) water and alcohol to which a small amount of ester, ketone, or
alkyl benzene is added.
26. A method as in claim 25 where said electrochromic compound is
selected from the group consisting of pyridine derivatives,
bipyridinium derivatives, phenazine derivatives, aminoquinone
derivatives, rhodamine derivatives, and diphthalocyanine
derivatives.
27. A method as in claim 26 where said electrochromic compound is
present within the range of 0.1 to 10 wt.% of said composition, and
preferably within the range of 1 to 5 wt.%.
28. A method as in claims 23 or 24 where the electrochromic
compound is alkyl bipyridinium salt, it being so reduced by said
additive compound that one mono anion thereof is trapped.
29. A method as in claim 28 where the number of mols of said
additive compound is no more than the number of mols of the mono
anion of the alkyl bipyridinium salt.
30. The composition as in claim 15 wherein said electrochromic
compound is selected from the group of compounds represented by the
formula; ##STR10## where Y is --CH.dbd.N--, --CH.dbd.CH--,
--C.tbd.C--, --N.dbd.N--, or ##STR11## and R.sub.1 and R.sub.2 are
alkyl radicals or alkoxy radicals, and X.sup.- is a mono anion.
31. A device as in claim 20 where said electrochromic compound is
selected from the group of compounds represented by the formula;
##STR12## where Y is --CH.dbd.N--, --CH.dbd.CH--, --C.tbd.C--,
--N.dbd.N--, or ##STR13## and R.sub.1 and R.sub.2 are alkyl
radicals or alkoxy radicals, and X.sup.- is a mono anion.
32. A method as in claim 25 where said electrochromic compound is
selected from the group of compounds represented by the formula;
##STR14## where Y is --CH.dbd.N--, --CH.dbd.CH--, --C.tbd.C--,
--N.dbd.N--, or ##STR15## and R.sub.1 and R.sub.2 are alkyl
radicals or alkoxy radicals, and X.sup.- is a mono anion.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an electrochromic composition and an
electrochromic display device using the same, and more particularly
to an electrochromic composition containing a compound selected
from the group consisting of ammonia, organic amine and alkali, and
a diffusion type electrochromic display device. The "diffusion
type" electrochromic display device is disclosed in United States
patent application Ser. No. 769,564 and will be defined
hereinafter.
2. Description of the Prior Art
Electrochromic compounds (hereinafter referred to as "EC compound")
present different colors depending upon the state of the compounds,
i.e. oxidized state or reduced state since the spectroscopic
absorption of the compounds differs depending upon the state
thereof. The EC compounds are divided into those coloring in a
reduced state and those coloring in an oxidized state. The EC
compounds coloring in a reduced state does not show a color or
shows a light color in an oxidized state and colors in a reduced
state. The EC compounds coloring in an oxidized state does not show
a color or shows a light color in a reduced state and colors in an
oxidized state.
The EC compounds sealed between a pair of electrodes at least one
of which is transparent present color changes when application of
an electric field thereacross is turned on and off. When the
solubility of the EC compound dissolved in a solvent of the EC
composition sealed between the pair of electrodes is low, the
displayed pattern is maintained for a long time, for instance,
several months. This kind of EC display device is called
memory-type EC display device. When the solubility of the EC
compound to the solvent is high, the displayed pattern quickly
disappears upon turning off the application of the electric field.
This kind of EC display device is disclosed in detail in a
copending U.S. patent application Ser. No. 769,564. This kind of
display device is called in said patent application "diffusion
type" EC display device. The diffusion type EC display device is
characterized in that between a pair of electrodes there is sealed
an EC composition coloring in a reduced state which is composed of
an EC compound and a solvent, the solubility of the EC compound to
the solvent being not less than 10.sup.-2 mol/100 g-solvent in a
reduced state and not less than 10.sup.-1 mol/100 g-solvent in an
oxidized state. The EC compound is sealed
The diffusion type EC display device is advantageous over the known
memory type EC display device (as disclosed in U.S. Pat. No.
3,854,794) in that the life time is longer, the response is higher,
the driving voltage can be lower, an erasing bias voltage need not
be applied, and the reference electrode need not be used.
In the diffusion type EC display device as described briefly above,
it is desired that the EC compound having a far clearer color and
stable color presentation be provided. It is further desired that
the EC display device have a far longer life and higher contrast of
the pattern displayed thereby.
In order to prepare a diffusion type EC display device, the EC
compound coloring in a reduced state must be sealed in a space
between a pair of electrodes in a reduced colored state. The method
for sealing the EC compound in the space in a reduced state is
disclosed in said patent application. For instance, the EC compound
coloring in a reduced state and a solvent are sealed in the space
in a reducing atmosphere as of hydrogen gas, or the EC compound
coloring in a reduced state and a solvent are sealed in the space
in an atmosphere of inert gas as of nitrogen gas and a high
potential (coloring potential) is applied to the electrodes to
convert the EC compound sealed in the space into the reducing
state.
The above described methods for sealing the EC compound in the
space between a pair of electrodes constituting the EC display
device suffer from the defects as follows. In the former method
utilizing hydrogen gas, the operation is very troublesome since all
the works should be conducted in the hydrogen gas and there is a
danger of combustion of the gas. In the latter method utilizing
nitrogen gas, the water in the solvent is electrolyzed by the high
potential and bubbles of gas generated by the electrolysis appear
in the display. In order to prevent the electrolysis, the potential
must be lowered and applied for a long time which results in
insufficient coloring.
SUMMARY OF THE INVENTION
The primary object of the present invention is to provide an EC
composition which presents clear and stable color that is suitable
for a diffusion type EC display device.
Another object of the present invention is to provide an EC
composition which elongate the life of the display device in which
the EC compound is used.
Still another object of the present invention is to provide an EC
composition which enhances the contrast of the image or pattern
displayed by the EC display device in which the EC compound is
used.
A further object of the present invention is to provide an EC
composition which can be sealed in a space between a pair of
electrodes without using a hydrogen gas atmosphere.
A still further object of the present invention is to provide an EC
composition which can be sealed in a space between a pair of
electrodes in an atmosphere of air or nitrogen gas and need not be
applied with a high coloring potential after sealed in such an
atmosphere.
A still another object of the present invention is to provide an EC
display device of diffusion type which has a long life and a high
contrast of the image or pattern displayed thereby.
The above objects of the invention are accomplished by providing an
EC composition comprising (a) a solvent, (b) an EC compound the
solubility of which to the solvent is not less than 10.sup.-2
mol/100 g-solvent in a reduced state and not less than 10.sup.-1
mol/100 g-solvent in an oxidized state, and (c) a compound selected
from the group consisting of ammonia, organic amine and alkali. The
above objects of the present invention are also accomplished by
providing an EC composition comprising (a) a solvent, (b) an EC
compound the solubility of which to the solvent is not less than
10.sup.-2 mol/100 g-solvent in a reduced state and not less than
10.sup.-1 mol/100 g-solvent in an oxidized state, (c) a compound
selected from the group consisting of ammonia, organic amine and
alkali, and (d) a masking agent. Further, the above objects
regarding the EC display device are accomplished by providing a
display element consisting of a pair of electrodes at least one of
which is transparent filled with said EC composition.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a cross sectional view of an EC display device in
accordance with an embodiment of the present invention,
FIG. 2 is a plan view of a front electrode plate of a preferred
embodiment of the EC display device in accordance with the present
invention, and
FIG. 3 is a cross sectional view of an empty EC display cell
employing the front electrode plate as shown in FIG. 2.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, a pair of electrode plates 11 and 12 are
oppositely disposed and are provided on the inner surface thereof
with electrode layers 13 and 14. Between the pair of oppositely
disposed electrode plates 11 and 12 is provided a spacer 15 to form
an enclosed space between the electrode plates 11 and 12. The space
enclosed with the spacer 15 and the electrode layers 13 and 14 on
the electrode plates 11 and 12 is filled with an EC composition 16.
The electrode plates 11 and 12 are provided with the electrode
layers 13 and 14 which are formed into the shape representing a
numeral "8" for instance to indicate numerals 0 to 9 as shown in
FIG. 2. In the embodiment shown in FIGS. 2 and 3, the electrode
plate 1 on one side of an EC display cell 20 is provided thereon
with seven-segment type display pattern elements 2 to 8 which form
a numeral "8" and lead wires 2a to 8a connected therewith. Further,
the electrode plate 1 is provided with a transparent film 10 which
is made of the same material as that of the electrode elements 2 to
8 and the lead wires 2a to 8a and covers the area not covered with
the electrodes and the lead wires in order to prevent the
electrodes and the lead wires from being observed when the driving
potential is not applied to the display device. As shown in FIG. 3,
electrodes 22 are deposited on a back electrode plate 21 at
positions facing to the front electrode elements 2 to 8. The front
and back electrode plates 1 and 21 are connected to each other by
means of a spacer 23 which encloses a space to be filled with an EC
composition therebetween. When the EC display device thus prepared
is viewed from front, the whole front area appears to be uniformly
in the same color or density.
In the EC display cell as described above, an EC composition as
described in detail hereinbelow is charged. Now the behavior and
composition of the EC composition will be described in detail
hereinbelow.
A well known organic EC compound, alkyl bipyridinium salt, is
capable of taking the following three kinds of states I, II and III
from one to another of which the EC compound is capable of
changing. ##STR1## (where R is an alkyl radical and X is a negative
ion of mono-valent).
As shown above, the alkyl bipyridinium salt is capable of
reversibly be reduced and oxidized. In the state (I), the salt is
solved in a solvent and presents no color and is transparent. In
the state (II) which is the first reduced state, it presents
purple-blue and has a solubility which is lowered as the number of
carbons of the alkyl radical is increased. In the state (III) which
is the second reduced state, the salt presents light yellow which
results in low contrast of the pattern displayed and has a
solubility which is lower than that of the salt in the state (II).
Further, the reversibility of the compound to the state (II) is
markedly lowered.
The diffusion type EC display device should be made so that the
alkyl bipyridinium salt is in the state (II) in its normal
condition in the sealed cell. Therefore, as seen from the above
described reaction formula, the salt should be sealed in the cell
with one mono anion trapped.
In accordance with this invention, the EC composition as described
hereinafter is simply put into the EC display cell in a proper
atmosphere as of air or nitrogen gas. It is unnecessary to seal the
cell in a reduced state. This is accomplished by adding a compound
selected from the group consisting of ammonia, organic amine and
alkali to the EC compound employed in the diffusion type EC display
device. In other words, by adding one of said compounds to the
normal EC compound, the EC compound is capable of coloring without
being sealed in a reduced state. The process of the coloring
behavior of the EC compound to which ammonia or organic amine is
added is considered to be based on the following chemical reaction.
##STR2## As shown above, by adding ammonia or organic amine to an
EC compound, a first reduced state in which the compound presents
purple-blue is obtained. The condition of the color can be
controlled by the amount of the ammonia or organic amine added.
However, if the amount of the ammonia or organic amine added to the
EC compound is larger than the number of mols of the mono anion of
the alkyl bipyridinium salt, the salt is wholly transferred to the
second reduced state as shown in the following reaction formula,
which results in low contrast of the pattern and poor reversibility
to the oxidized state. ##STR3## From the above mentioned reason,
the amount of the ammonia or organic amine added to the EC compound
should be made less than that required for completely trapping the
mono anions carried by the alkyl bipyridinium salt in case that the
EC compound has two different reduced states like the aforesaid
alkyl bipyridinium salt. When the EC compound does not have a
plurality of reduced states as alkyl phenazine salt or when the
plurality of reduced states are all properly utilized as the state
of display, the amount of the ammonia or organic amine is not
limited as above.
When alkali is added to the EC compound, the similar coloring state
is obtained without using a hydrogen atmosphere or applying a high
coloring potential after sealing in an inert atmosphere, although
the chemical process for effecting the coloring state is not
clarified. Further, in this case also, the condition of the color
is controlled by changing the amount of alkali. This was confirmed
by a number of tests.
As the EC compound to be used in the EC composition of this
invention, can be used pyridine derivatives, bipyridinium
derivatives, phenazine derivatives, aminoquinone derivatives,
rhodamine derivatives, diphthalocyanine derivatives, and compounds
represented by the formula: ##STR4## where Y is --CH.dbd.N--,
--CH.dbd.CH--, --C.tbd.C--, --N.dbd.N--, ##STR5## etc, and R.sub.1
and R.sub.2 are alkyl radial or alkoxy radical, and X.sup.- is mono
anion.
The solubility of the EC compound used in the EC composition of
present invention should not be less than 10.sup.-2 mol/100
g-solvent in a reduced state and not less than 10.sup.-1 mol/100
g-solvent in an oxidized state.
The amount of the EC compound to be contained in the EC composition
of the present invention should be within the range of 0.1 to 10
wt.% of the whole EC composition, and preferably within the range
of 1 to 5 wt.%. When the amount is falls below 0.1 wt.% the
contrast of the displayed pattern is lowered and the life time is
shortened. When it exceeds 10 wt.%, no change in effect is
observed. Therefore, in order to save the amount of the EC
compound, 10 wt.% is enough to obtained the aimed results.
As the solvent to be used in the EC composition of this invention,
water, mixture of water and alcohol, mixture of water and alcohol
to which a little amount of ester, keton, or alkyl benzene, etc.
can be used. The alcohol is a compound in which hydrogens of
aliphatic hydrocarbons, ring compounds or side chains are
substituted by hydrooxyl groups. Particularly, divalent or
trivalent alcohol such as ethylene glycol or glycerol is preferred.
The above mentioned multivalent alcohols are preferred to be
contained in the amount of 70 wt% or more of the whole solvent so
that a sufficient amount of water be contained in the hydrophilic
multivalent alcohol. Further, to the above solvent, inorganic salt
such as KBr and NaCl or organic salt may be added as an
electrolyte.
The aforesaid organic amine to be used in the composition of this
invention is a compound in which hydrogen atoms of ammonium
represented by NH.sub.3 are substituted by hydrocarbon radicals
(R), such as primary amine, secondary amine and tertiary amine of
aliphatic group, alicyclic group and aromatic group, and compound
containing a combination of primary amine and secondary amine.
The primary amine of aliphatic group is represented by a general
formula of R--NH.sub.2 and is, for example, methyl amine, ethyl
amine, propyl amine, isopropyl amine, butyl amine, amylamine, hexyl
amine, heptyl amine, octyl amine, nonyl amine, decyl amine, undecyl
amine, dodecyl amine, tetradecyl amine, pentadecyl amine, cetyl
amine, etc.
The secondary amine of aliphatic group is represented by a general
formula of ##STR6## and is, for example, dimethyl amine, diethyl
amine, dipropyl amine, diisopropyl amine, dibutyl amine, diamyl
amine, etc.
The tertiary amine of aliphatic group is represented by a general
formula of ##STR7## and is, for example, trimethyl amine, triethyl
amine, tripropyl amine, tributyl amine, triamyl amine, etc.
Although the R, R', R" have been described as saturated alkyl group
of straight chain and ramified chain, these may be aliphatic
unsaturated amine such as arylamine, diaryl amine, and triaryl
amine or may be amine in which a part of alkyl group is substituted
by hydroxyl group, nitro group, carboxyl group, cyano group, keton
or ester.
Further, it may be a compound in which molecules primary amine and
secondary amine exist like triethylene tetramine. Further,
alicyclic amine such as cyclopropyl amine, cyclobutyl amine,
cyclopentyl amine, and cyclohexyl amine can be used.
As the aromatic amine can be used primary amine of aromatic group
such as aniline, O-toluidine, m-toluidine, p-toluidine, benzyl
amine, .alpha.-naphtyl amine, .beta.-naphtyl amine, etc., secondary
amine of aromatic group such as methyl aniline, ethyl aniline,
dibenzyl amine, diphenyl amine, etc., and tertiary amine of
aromatic group such as dimethyl aniline, diethyl aniline, tribenzyl
amine,, triphenyl amine, etc.
On the other hand, the alkali to be used in the composition of this
invention is a substance which dissolves in water such as alkali
metal hydroxide, ammonium hydroxide, sodium carbonate, ammonium
carbonate and sodium phosphate. Among these examples of alkali
sodium hydroxide and potassium hydroxide are preferred in view of
the resulting contrast of the image obtained and the life time.
The added amount of ammonia, organic amine and alkali should be
changed according to the kind of the EC compound employed.
Generally, the amount of these additives should preferably be
within the range of 1/2 to 3/2 mol. Among the additives as
mentioned above, ammonia and organic amine are preferred from the
viewpoint of the resulting contrast of display, stability of
display and life time. Particularly, the organic amine is preferred
in this respect. This is considered to be based on the difference
in process in trapping the mono anion as shown in said reaction
Now a detailed description of the organic amine to be used in the
EC composition of the present invention will be made hereinbelow.
The effect of the organic amine to color the EC compound depends
upon the kinds of the amine and the kinds of the EC compound used
in combination with the amine. When the effect is great, the EC
display device of diffusion type can be simply obtained by only
filling the EC display cell with the EC composition containing the
amine. When the effect is low, the EC composition is first sealed
in the cell and then a coloring potential is applied to the cell to
color the EC composition. However, even in this case, the level of
the coloring potential can be markedly lowered in comparison with
the conventional EC composition in which no amine is contained. The
great effect of coloring the EC compound is obtained in case of the
primary amine of aliphatic group and then the secondary amine of
aliphatic group. The effect is lowered in the order of the tertiary
amine of aliphatic group, the primary amine of aromatic group, the
secondary amine of aromatic group and the tertiary amine of
aromatic group.
In case that water soluble amine or ammonia is used, the pH of the
solution is increased as well as the trapping effect is obtained
which results in high effect of coloring the EC compound.
Particularly when acid salt EC compound which makes a water
solution thereof acid is used, the pH is increased to neutral or
alkali by using said water soluble amine, whereby the deterioration
of the electrode provided in the display cell is prevented and a
stable EC display device can be obtained.
The above water soluble amine is for instance hydrocarbon groups
(R) having a small number of carbon atoms or partly substituted by
hydrophilic groups like --OH or --COOH.
In the EC composition in accordance with the present invention, a
masking agent can be further contained besides said composition
components of solvent, EC compound and additive such as amine. As
the masking agent can be used any kind of fine particles so long as
the rear electrode is optically hindered thereby. Normally, various
kinds of pigment are used as the masking agent whether they are
organic or inorganic. The masking agent must be stable in the EC
composition and have a sufficient masking effect. From this reason,
metal pigments and extender pigments are not suitable for the
masking agent. The color of the pigments is selected depending upon
the color of the EC compound.
As the inorganic pigments can be used white pigments such as
titanium oxide, zinc sulfide and lithopone, black pigments such as
carbon black and graphite, red pigments such as red lead and
cadmium red, yellow pigments such as chrome yellow, zinc yellow and
cadmium yellow, blue pigments such as prussian blue, ultramarine
and cobalt blue, green pigments such as chrome green, emerald green
and zinc green, and brown pigments such as iron oxide and red
oxide. As the organic pigments can be used yellow-2, yellow-3,
orange-5, red-3, and red-4 in the C.I.Name. Among these pigments,
the white pigment as of titanium oxide is preferred from the
viewpoint of masking effect and stability of display.
The amount of the masking agent to be contained in the EC
composition of the present invention depends upon the masking
effect thereof, which is normally within the range of 10 to 70 wt.%
of the whole composition. When the spacing between the oppositely
faced electrode plates is several tens to several thousands of
microns, the amount of the masking agent is preferred to be within
the range of 30 to 70 wt.%, and more preferably from the viewpoint
of stability of display and prevention of sedimentation within the
range of 40 to 60 wt.%.
The structure of the EC display device in which the above described
EC composition is to be sealed is as described hereinbefore with
reference to the accompanying drawings. Further, the structure is
disclosed for instance in British Pat. No. 1,427,489 and U.S. Pat.
No. 3,451,741.
When the above described diffusion type EC display device is used
as a transmission type display device, the electrodes plates 1 and
21 are made transparent and an EC composition which does not
contain the masking agent is put into the display cell. When a
reflection type EC display device is to be made, the EC composition
containing the masking agent is used or a porous opaque film such
as a filter paper is put into the display cell and the EC
composition which does not contain the masking agent is used.
Particularly in the diffusion type EC display device, a reflection
type display device using the EC composition containing the masking
agent gives a good result from the viewpoint of response and
stability of display.
Now the preferred embodiments of the present invention will be
described in detail with reference to the results of tests of
actual examples made in accordance with the present invention. In
the following embodiments, the EC composition contains a masking
agent or a porous opaque film. It should be understood, however,
that the present invention is not limited to these embodiments.
EXAMPLE 1
5 wt.% of .gamma., .gamma.'-dimethyl bipyridinium dibromide (EC
compound), 40 wt.% of ethylene glycol, 4 wt.% of distilled water,
47 wt.% of titanium oxide (TiO.sub.2), 3 wt.% of gelatin and 1 wt.%
of defoaming agent plus dispersing agent were mixed and stirred in
a ball mill the interior of which was substituted by nitrogen gas
for 24 hours, and then butyl amine was added to 10 g of the
composition in an atmosphere of nitrogen gas. The amount of the
butyl amine added to the EC composition as an organic amine was
changed as 7.25.times.10.sup.-4 mol (half in mol number of the EC
compound), 1.45.times.10.sup.-3 mol (same in mol number of the EC
compound), 2.17.times.10.sup.-3 mol (1.5 times in mol number as
many as that of EC compound), and 2.9.times.10.sup.-3 mol (twice in
mol number as many as that of EC compound). By adding the butyl
amine to the EC composition as prepared above, the EC composition
was colored into blue.
The composition thus prepared was put into an EC display cell
composed of a pair of glass plates having a thickness of 3 mm
carrying thereon a transparent electrode layer vacuum evaporated of
indium oxide having a surface resistance of 10.OMEGA./cm.sup.2
oppositely disposed with a spacing of 100.mu.. After the EC
composition was put into the cell, the inlet used for putting in
the composition was sealed by use of a soft metal. Thus, a
diffusion type EC display device was prepared. The degree of
coloring at the time the EC display device was prepared was named
initial coloring degree. The cell was then applied with a driving
potential of 1 volt of DC power which was periodically inverted at
time interval of 1 second. The EC display device in which the
initial coloring degree was low was changed to present a high
coloring degree after 30 minutes of application of the periodically
inverting DC potential. The sequential change of the coloring
degree effected by the application of the potential was measured to
know a coloring time.
When the amount of the butyl amine added to the EC composition was
7.25.times.10.sup.-4 mol to the 10 g of the composition, the
coloring degree was about 70% which was considered to be the
maximum in which almost all .gamma.,.gamma.'-dimethyl bipyridinium
bromide was converted to the reduced state (coloring degree:B) and
the color had a long life of 10.sup.7 times or more of inversion of
the applied potential in the above mentioned method of driving
(life:++).
When the amount of the butyl amine was 1.45.times.10.sup.-3 mol and
2.17.times.10.sup.-3 mol, the initial coloring degree was almost
maximum (A) and the life was 10.sup.7 times or more (++). When the
amount was 2.9.times.10.sup.-3 mol, the initial coloring degree was
almost maximum (A) but the life was about 10.sup.4 times (-) which
means the color was changed from purple blue to light yellow when
the applied potential was inverted about 10.sup.4 times.
The butyl amine was named Sample No. 1 and various other amines
were tested in the sample names as follows.
______________________________________ Sample No. Name of amines
______________________________________ 2 nonyl amine 3
2-amino-2-methyl-1-propanol 4 dipropyl amine 5 dibutyl amine 6
triethyl amine 7 tripropyl amine 8 diaryl amine 9 cyclohexyl amine
10 aniline 11 dimethyl amine 12 benzyl aniline 13 triethylene
tetramine 14 p-amino-diphenyl amine
______________________________________
The results of the tests of these samples are shown in the table
below. As shown in the table, the amount of the organic amine added
to the EC compound is preferred to be within the range of 1/2 to
3/2 times in terms of mol number as many as that of the EC
compound. Further, when the organic amine was not added to the EC
compound, the coloring potential required to be applied to the cell
to obtain the initial coloring degree of (A) was 1.85 V, which was
lowered to 1.0 V by adding organic amine to the EC compound.
In the following table initial coloring degree is ranked from A to
D, and the life is ranked from (++) to (-) as follows.
Initial coloring degree:
A: sufficient coloring (100%)
B: almost maximum coloring (70%)
C: lowered coloring (40%)
D: faintly coloring (10%)
Life of Coloring:
++: color not faded after 10.sup.7 times of inversion of DC1 V at 1
second cycle
+: color not faded after 10.sup.6 times of inversion
-: color not faded after 10.sup.4 times of inversion
TABLE ______________________________________ 7.25 .times. 10.sup.-4
1.45 .times. 10.sup.-3 2.17 .times. 10.sup.-3 2.9 .times. 10.sup.-3
Sam- mol mol mol mol ple Init. Init. Init. Init. No. Color Life
Color Life Color Life Color Life
______________________________________ 1 B ++ A ++ A ++ A - 2 B ++
A ++ A ++ A - 3 B ++ A ++ A ++ A + 4 C ++ B ++ B ++ A + 5 C ++ B ++
B ++ A + 6 C ++ C ++ C ++ B + 7 C ++ C ++ C ++ B + 8 C ++ C ++ C ++
B + 9 B ++ B ++ A ++ A - 10 C ++ C ++ B ++ A + 11 D ++ D ++ C ++ B
+ 12 B ++ B ++ A ++ A + 13 B ++ B ++ A ++ A + 14 C ++ C ++ B ++ B +
______________________________________
EXAMPLE 2
As the EC compound, .gamma.,.gamma.-di(p-cyanophenyl)bipyridinium
bromide was used and 2.17.times.10.sup.-3 mol of butyl amine was
added to the EC compound in the same process as that employed in
EXAMPLE 1. Consequently, the EC composition colored into green. The
EC display device using thus obtained composition was tested by the
same method as that employed in Example 1, which resulted in long
life of more than 10.sup.7 times.
EXAMPLE 3
As the EC compound, methylphenazine bromide was used and
2.17.times.10.sup.-3 mol of butyl amine was added thereto, which
resulted in coloring into green. The measured life was more than
10.sup.7 times.
EXAMPLE 4
As the EC composition was used a composition composed of 5 wt.% of
.gamma.,.gamma.'-bipyridinium hydrochloride ##STR8## 35 wt.% of
ethylene glycol, 9 wt.% of distilled water, 47 wt.% of titanium
oxide (TiO.sub.2), 3 wt.% of gelatin, and 1 wt.% of defoaming agent
and dispersing agent. The pH of the composition was 3. The
composition having such a high acidity had not been used in the
conventional art because of its affect on the transparent electrode
plates as of indium oxide and tin oxide. However, by adding thereto
butyl amine, the composition was colored into blue and the pH was
increased to 7. At the pH of 6.8, the composition started coloring
and at the pH of 7 the composition was sufficiently colored into
favorable blue. The colored composition was used to made an EC
display device in the same manner as that employed in EXAMPLE 1.
The results of the test showed that the transparent electrodes were
not damaged by the composition. Thus, by adding the water soluble
amine to the EC compound, it was made possible to use acid salt EC
compounds as the EC compounds filling the EC display cell.
EXAMPLE 5
An aqueous solution (28%) was added to the EC compound as used in
EXAMPLE 1 in the amount of 2.17.times.10.sup.-3 mol when calculated
in terms of ammonia, so that the EC compound was colored into
purple blue. The EC compound thus prepared was used to make an EC
display device. The life was more than 10.sup.7 times.
EXAMPLE 6
7 wt.% of .gamma.,.gamma.'-dimethyl bipyridinium bromide, 72 wt.%
of ethylene glycol. 15 wt.% of distilled water, 5 wt.% of gelatin
and 1 wt.% of defoaming agent were mixed and stirred together. To
10 g of the composition thus prepared was added 0.05 g of KBr and
2.17.times.10.sup.-3 mol of butyl amine, so that the composition
was colored into blue.
Thus prepared EC composition was put into an EC display cell as
used in EXAMPLE 1. Further, in the cell was provided a porous
opaque film having a thickness of 50.mu. (Membrane Filter TM-2;
made by Toyo Roshi K.K.). Then, the aperture through which the EC
composition was charged in the cell was sealed by a soft metal. The
DC display device thus prepared showed favorable color and
life.
EXAMPLE 7
To the EC compound as used in EXAMPLE 1 was added alkali to make it
colored into blue in the amount of 7.25.times.10.sup.-4 mol (1/2
times in mol number), 2.17.times.10.sup.-3 mol (3/2 times) and
2.0.times.10.sup.-3 mol (twice). As the alkali was used, sodium
hydroxide (Sample No. 1), potassium hydroxide (Sample No. 2),
lithium hydroxide (Sample No. 3) and sodium carbonate (Sample No.
4). The results obtained are shown in the following table in the
same manner as that employed in the first table showing the results
of EXAMPLE 1
TABLE ______________________________________ 7.25 .times. 10.sup.-4
2.17 .times. 10.sup.-3 2.9 .times. 10.sup.-3 mol mol mol Init.
Init. Init. Sample No. Color Life Color Life Color Life
______________________________________ 1 B ++ A + A - 2 B ++ A + A
- 3 C ++ B - B - 4 C ++ B - B -
______________________________________
EXAMPLE 8
As the EC compound was used .gamma.,.gamma.'-di(p-cyanophenyl)
bipyridinium bromide was used. 2.17.times.10.sup.-3 mol of sodium
hydroxide was added to make the EC compound color in green. The
life measured was more than 10.sup.6 times.
EXAMPLE 9
As the EC compound was used methylphenazine bromide and
2.17.times.10.sup.-3 mol of sodium hydroxide was added to the EC
compound to make it color in green. The life measured was more than
10.sup.7 times.
EXAMPLE 10
Instead of the butyl amine added to the composition prepared in
EXAMAPLE 6, the same amount of potassium hydroxide was added. The
results were quite the same as those obtained in EXAMPLE 6 in the
obtained color and in the life of the display device made by use
thereof together with the membrane filter as used in EXAMPLE 6.
EXAMPLE 11
Similarly to EXAMPLE 1, to an EC composition prepared according to
EXAMPLE 1 were added 1.45.times.10.sup.-3 mol of
2-amino-2-methyl-1-propanol, 1.45.times.10.sup.-3 mol of ammonia
(in the form of aqueous ammonia of 28% concentration), and
1.45.times.10.sup.-3 mol of sodium hydroxide separately. These
samples were named Sample A, B and C, respectively. These samples
were tested of their life and durability by an acceleration test in
which D.C. 1 volt was continuously applied to the samples. Sample A
did not change at all after 10.sup.3 hours passed. Sample B showed
uneveness in density of displayed pattern on the cathode when
8.times.10.sup.2 hours passed. Sample C showed the defect similar
to that of Sample B when 50 hours passed. These results show that
the organic amine is the most preferred from the viewpoint of the
life of the EC display device in which the additive was used. The
second preferred additive was found to be ammonia and the third was
alkali.
* * * * *